US3026285A - Curing agent comprising the reaction product of an aliphatic polyamine and an aldehyde, and epoxy resin cured therewith - Google Patents

Curing agent comprising the reaction product of an aliphatic polyamine and an aldehyde, and epoxy resin cured therewith Download PDF

Info

Publication number
US3026285A
US3026285A US840788A US84078859A US3026285A US 3026285 A US3026285 A US 3026285A US 840788 A US840788 A US 840788A US 84078859 A US84078859 A US 84078859A US 3026285 A US3026285 A US 3026285A
Authority
US
United States
Prior art keywords
aldehyde
epoxy resin
reaction product
acid
mols
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US840788A
Inventor
Frank N Hirosawa
Delmonte John
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Individual
Original Assignee
Individual
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Priority to US840788A priority Critical patent/US3026285A/en
Application granted granted Critical
Publication of US3026285A publication Critical patent/US3026285A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
    • C08G59/4014—Nitrogen containing compounds
    • C08G59/4042—Imines; Imides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins

Definitions

  • This invention relates to curing agents for epoxy resins and in particular to curing agents which are non-irritating to the skin of persons handling the resin mixtures.
  • the low temperature curing agents presently used in hardening 2,2 bis (4-hydroxyphenyl) propane-epichlorohydrin epoxy resins are primary irritants and cause skin irritation and subsequent sensitization of persons handling the materials. In consequence, elaborate precautions have been required in the handling of epoxy resins and in particular the low (room) temperature curing agents therefor.
  • a substantially non-irritating curing agent is produced by pre-reacting a mixture of polyamine and an aldehyde, by which there is formed a complex of undetermined structure. Water is liberated in this reaction, and there is a small increase in viscosity under the reacting conditions used.
  • This amine-aldehyde complex not only is non-irritating in its effect upon humans handling it, but also it has superior hardening properties in epoxy resin compositions.
  • the viscosity of our curing agent may be controlled by the subsequent reaction of the amine aldehyde complex with an aliphatic acid or acid anhydride.
  • the acid anhydrides are preferred because less water is evolved in the reaction, and therefore there is less water to be removed in processing the curing agent.
  • the acid or acid anhydride also improves the chemical and water resistance of the curing agent as well as the cured epoxy resin products, as compared to polyamine curing agents and polyamine cured epoxy resins.
  • EXAMPLE 1 Two mols of triethylenetetramine and one rnol of paraformaldehyde were reacted to produce an amine-aldehyde complex.
  • the polyamine was heated to 70 C. in a flask, with continuous agitation, the flask being equipped with a vacuum take-off, so that the water formed in the reaction may be removed.
  • the paraformaldehyde was then added slowly, maintaining the temperature at about 120 C. for about one-half hour. Upon cooling, the product had a viscosity of 71 centipoises and was nonirritating and had good hardening properties for epoxy resins.
  • polyamines which have been successfully used in reactions forming our non-irritant hardener similar to those of Examples 1 to 5 are ethylene diamine; hydrazine; 1,3- and 1,2-propanediamine; 1,4-butanediamine; trimethylenediarnine; tetramethylenediamine; diethylenetriamine; triethylene tetramine; te-traethylenepentamine; 3,3-iminobisproplyamine; 3,3'-(methylimino)bispropylamine; 3-isopropylaminopropylamine; dimethylaminopropylamine; diethylaminopropylamine; ethylenebisoxypropylamine; methanediarnine; and metaxylenediamine.
  • paraformaldehyde is the most convenient and preferred aldehyde material for use in making the aminealdehyde complex
  • other aldehydes such as formaldehyde (formalin or paraformaldehyde), acetaldehyde (paraldehyde), propionaldehyde, butyraldehyde, furfural, benzaldehyde, glyoxal, pyruvic aldehyde, crotonaldehyde, acrolein, and methylacrolein may be used in forming nonirritant aminealdehyde complexes for use as epoxy resin hardeners.
  • the ratio of amine to aldehyde is selected so that at least one active hydrogen of each amine will be reacted with the aldehyde; that is, no free aminm must be present in which none of their hydrogens have been reacted, either with aldehyde or an acid anhydride.
  • the preferred ratio is in the range of two mols of polyamine to one mol of aldehyde, and one mol of polyamine to two mols of aldehyde.
  • the viscosities of the amine-aldehyde complex compositions formed as in the above illustrative examples may be controlled by further reacting the complexes with carboxylic acids or acid anhydn'des.
  • the ratio of anhydride or acid to amine-aldehyde product is selected to give the desired viscosity while avoiding tying up all of the potentially available reactive hydrogen groups which should be available to initiate the curing reaction when the hardener is subsequently used with the epoxy resin. See Examples 7 to 16.
  • EXAMPLE 7 The amine-aldehyde complex as formed by the steps disclosed in Example 1 may be further improved by reacting it with a carboxylic acid or the anhydride of the acid. After the mixture of aldehyde and amine had been heated for about one-half hour or until all of the formaldehyde had reacted, about 0.75 mol of hexahydrophthalic 3 acid was added slowly, maintaining the temperature at about 150 C. This was continued for about one-half hour, using a reduced pressure on the reaction vessel of about 100 mm. mercury to remove the water formed. A Water-free product having a viscosity of 4660 centipoises (measured at 25 C.) was produced.
  • EXAMPLE 8 Proceeding in a similar way to Example 7, an aminealdehyde-anhydride composition consisting of the reaction product of 8 mols of triethylenetetramine and 4 mols of paraformaldehyde, followed by the subsequent reaction with one mol of dodecenyl succinic anhydride gave a nonirritating hardener composition having a viscosity of 200 centipoises.
  • EXAMPLE 9 EXAMPLE l Proceeding as in Example 7, the reaction product of 4 mols of tetraethylenepentamine and 2 mols of paraformaldehyde, followed by the subsequent reaction with one mol of hexahydrophthalic anhydride, yielded a nonirritant hardener composition having a viscosity of 15,000 centipoises at 25 C.
  • EXAMPLE 17 One hundred parts by weight of an active 2,2 bis (4- hydroxyphenyl) propane-epichlorohydrin epoxy resin having an epoxy equivalent of 200 were mixed with 200 parts by weight of the hardener prepared as described in Example 7. T he gelling time at 25 C. was 30 minutes, and the composition was hardened completely in the usual manner.
  • non-irritant epoxy hardeners While specific examples of non-irritant epoxy hardeners have been given by Way of illustration, it will be understood that many other combinations of equivalent ingredients may be reacted to give non-irritant hardening agents for epoxy resins, within the scope of the appended claims.
  • a non-irritant hardening agent adapted for curing 2,2-bis (4-hydroxyphenyl) propane-epichlorohydrin epoxy resin compositions consisting essentially of the substantially anhydrous liquid reaction product of an aliphatic polyamine compound and an aldehyde, the ratio of amine to aldehyde being selected to retain a substantial proportion of reactive hydrogen in the product.
  • a non-irritant hardening agent adapted for curing epoxy resin compositions consisting essentially of the substantially anhydrous liquid reaction product of two mols of an aliphatic polyamlne compound and at least one mol of an aldehyde.
  • a non-irritant hardening agent adapted for curing 2,2-bis (4-hydroxyphenyl) propane-epichlorohydrin epoxy resin compositions consisting essentially of the co-reacted substantially anhydrous mixture of the liquid reaction product of an aliphatic polyamine with an aldehyde, and an acid constituent selected from the group consisting of aliphatic carboxylic acids, aromatic vcarboxylic acids, anhydrides of aliphatic carboxylic acids, and anhydrides of aromatic carboxylic acids; the ratio of acid anhydride or acid to the liquid reaction product being selected to retain a substantial proportion of reactive hydrogen in the hardening agent.
  • a non-irritant hardening agent adapted for curing 2,2 bis (4 hydroxyphenyl) propane epichlcrohydrin epoxy resin compositions consisting essentially of the coreacted substantially anhydrous mixture of the liquid reaction product of two mols or an aliphatic polyamine with at least one mole of. an aldehyde, and an acid constituent selected from the group consisting of aliphatic carboxylic acids, aromatic carboxylic acids, anhydrides of aliphatic carboxylic acids, and anhydrides of aromatic carboxylic acids, the ratio of the acid constituent to the amine-aldehyde reaction product being selected to produce a hardener agent of the desired viscosity and retained reactive hydrogen.
  • aldehyde is paraformaldehyde and the polyamine is selected from the group consisting of ethylene diamine; hydrazine; li -propanediamine; l,2-propanediamine; 1,4- butanediamine; 'trimethylenediamine; tetramethylenediamine; diethylenetriamine; triethylene tetramine; te aethylenepe ntarnine; 3,3'-irninobispropylamine; 3,3 (methylimino) bispropylamine; 3-isopropylamincpropylamine; dimetl'iylaminopropylamine; diethylaminopropylamine;
  • a hardened epoxy resin product consisting essenfially of a 2,2-bis (4-hydroxyphenyl) propane-epichlorohydrin epoxy resin and a hardener consisting essentially of the substantially anhydrous liquid reaction product of one mol of an aliphatic polyamine and at least one mol of an aldehyde, the epoxy resin and the hardener being present in substantially stoichiometrie proportions based upon the epoxy equivalent.
  • a hardened epoxy resin product consisting essentially of a 2,2-bis (4-hydroxyphenyl propane-epichlorohydrin epoxy resin, and a hardener consisting essentially of a co-reacted substantially anhydrous liquid reaction product of an aliphatic polyamine with an aldehyde, and a carboxylic acid constituent selected from the group consisting of aliphatic carboxylic acids, aromatic carboxylic acids, anhydrides of alphatic carboxylic acids, and anhydrides of aromatic carboxylic acids, the epoxy resin and the hardener being present in substantially stoichiometric proportions based upon the epoxy equivalent.
  • a non-irritant hardening agent adapted for curing 2,2-bis (4-hydroxyphenyl) propane-epichlorohydrin epoxy resin compositions consisting essentially of the substantially anhydrous liquid reaction product of tetraethylene pentamine andparaformaldehyde.

Description

k new United States Patent 3,526,285 a CURING AGENT COMPRISING THE REACTION PRODUCT OF AN ALIPHATIC POLYAMINE AND AN ALDEHYDE, AND EPOXY RESIN CURED THEREWITH Frank N. Pirosawa, 2839 Blanchard St., Los Angeles, Calif., and John Delmonte, 1637 Don Carlos Ave., Glendale, Calif. No Drawing. Filed Sept. 18, 1959, Ser. No. 840,788 14 Claims. (Cl. 260-452.)
This invention relates to curing agents for epoxy resins and in particular to curing agents which are non-irritating to the skin of persons handling the resin mixtures.
The low temperature curing agents presently used in hardening 2,2 bis (4-hydroxyphenyl) propane-epichlorohydrin epoxy resins, including the alipathic polyamines and adducts containing polyamines, are primary irritants and cause skin irritation and subsequent sensitization of persons handling the materials. In consequence, elaborate precautions have been required in the handling of epoxy resins and in particular the low (room) temperature curing agents therefor.
We have discovered that a substantially non-irritating curing agent is produced by pre-reacting a mixture of polyamine and an aldehyde, by which there is formed a complex of undetermined structure. Water is liberated in this reaction, and there is a small increase in viscosity under the reacting conditions used. This amine-aldehyde complex not only is non-irritating in its effect upon humans handling it, but also it has superior hardening properties in epoxy resin compositions. We have further discovered that the viscosity of our curing agent may be controlled by the subsequent reaction of the amine aldehyde complex with an aliphatic acid or acid anhydride. The acid anhydrides are preferred because less water is evolved in the reaction, and therefore there is less water to be removed in processing the curing agent. The acid or acid anhydride also improves the chemical and water resistance of the curing agent as well as the cured epoxy resin products, as compared to polyamine curing agents and polyamine cured epoxy resins.
The non-irritant nature of our hardener product was determined not only by the practical test of using the material, observing that without taking the usual precautions, no cases of skin irritation were encountered among the workmen using it, but also the material has been certified as non-irritating by a recognized dermatological laboratory.
EXAMPLE 1 Two mols of triethylenetetramine and one rnol of paraformaldehyde were reacted to produce an amine-aldehyde complex. The polyamine was heated to 70 C. in a flask, with continuous agitation, the flask being equipped with a vacuum take-off, so that the water formed in the reaction may be removed. The paraformaldehyde was then added slowly, maintaining the temperature at about 120 C. for about one-half hour. Upon cooling, the product had a viscosity of 71 centipoises and was nonirritating and had good hardening properties for epoxy resins.
EXAMPLE 2 When equal rnol proportions of triethylenetetramine and paraformaldehyde were reacted as in Example 1, a nonirrltating hardenin product having a viscosity of 205 centipoises was produced.
EXAMPLE 3 When the proportions of triethylenetetramine and paraformaldehyde were 4 mols amine to 3 mols of aldehyde,
3,026,285 Patented Mar. 20, 1962 the non-irritating hardener reaction product has a viscosity of 10S centipoises.
EXAMPLE 4 When 2 mols of diethylenetriamine were substituted for the amine of Example 1, a similar non-irritant epoxy hardener product was obtained having a viscosity of 50 centipoises.
EXAMPLE 5 When 2 mols of tetraethylenepentamine were substituted for the amine of Example 1, a similar product was obtained having a viscosity of centipoises.
EXAMPLE 6 When furfuraldehyde was substituted for the formaldehyde in Example 2, and the ingredients reacted, a nonirritant hardener product having a viscosity of 280 centipoises at 25 F. was produced.
Other polyamines which have been successfully used in reactions forming our non-irritant hardener similar to those of Examples 1 to 5 are ethylene diamine; hydrazine; 1,3- and 1,2-propanediamine; 1,4-butanediamine; trimethylenediarnine; tetramethylenediamine; diethylenetriamine; triethylene tetramine; te-traethylenepentamine; 3,3-iminobisproplyamine; 3,3'-(methylimino)bispropylamine; 3-isopropylaminopropylamine; dimethylaminopropylamine; diethylaminopropylamine; ethylenebisoxypropylamine; methanediarnine; and metaxylenediamine.
While paraformaldehyde is the most convenient and preferred aldehyde material for use in making the aminealdehyde complex, other aldehydes such as formaldehyde (formalin or paraformaldehyde), acetaldehyde (paraldehyde), propionaldehyde, butyraldehyde, furfural, benzaldehyde, glyoxal, pyruvic aldehyde, crotonaldehyde, acrolein, and methylacrolein may be used in forming nonirritant aminealdehyde complexes for use as epoxy resin hardeners.
The ratio of amine to aldehyde is selected so that at least one active hydrogen of each amine will be reacted with the aldehyde; that is, no free aminm must be present in which none of their hydrogens have been reacted, either with aldehyde or an acid anhydride. The preferred ratio is in the range of two mols of polyamine to one mol of aldehyde, and one mol of polyamine to two mols of aldehyde.
As further disclosed below, when an acid anhydride is also employed, some free amine hydrogens may be reacted with an acid or anhydride; for example, three mols of polyamine may be reacted with one mol of paraformaldehyde, and this reaction product further reacted as to one free mol of polyamine with an acid or acid anhydride. Thus, in every molecule of amine at least one active hydrogen of at least one terminal amino group must be reacted.
The viscosities of the amine-aldehyde complex compositions formed as in the above illustrative examples may be controlled by further reacting the complexes with carboxylic acids or acid anhydn'des. The ratio of anhydride or acid to amine-aldehyde product is selected to give the desired viscosity while avoiding tying up all of the potentially available reactive hydrogen groups which should be available to initiate the curing reaction when the hardener is subsequently used with the epoxy resin. See Examples 7 to 16.
EXAMPLE 7 The amine-aldehyde complex as formed by the steps disclosed in Example 1 may be further improved by reacting it with a carboxylic acid or the anhydride of the acid. After the mixture of aldehyde and amine had been heated for about one-half hour or until all of the formaldehyde had reacted, about 0.75 mol of hexahydrophthalic 3 acid was added slowly, maintaining the temperature at about 150 C. This was continued for about one-half hour, using a reduced pressure on the reaction vessel of about 100 mm. mercury to remove the water formed. A Water-free product having a viscosity of 4660 centipoises (measured at 25 C.) was produced.
EXAMPLE 8 Proceeding in a similar way to Example 7, an aminealdehyde-anhydride composition consisting of the reaction product of 8 mols of triethylenetetramine and 4 mols of paraformaldehyde, followed by the subsequent reaction with one mol of dodecenyl succinic anhydride gave a nonirritating hardener composition having a viscosity of 200 centipoises.
EXAMPLE 9 EXAMPLE l Proceeding as in Example 7, the reaction product of 4 mols of tetraethylenepentamine and 2 mols of paraformaldehyde, followed by the subsequent reaction with one mol of hexahydrophthalic anhydride, yielded a nonirritant hardener composition having a viscosity of 15,000 centipoises at 25 C.
EXAMPLE 1 l Proceeding as in Example 7, the reaction product of 6 mols of diethylenetriamine, and 3 mols of formaldehyde, followed by the subsequent reaction of 1 mol of acetic anhydride, yielded a low viscosity, non-irritant, eifective curing agent for epoxy resins.
EXAMPLE 12 Proceeding as in Example 7, the reaction product of 6 mols of triethylenetetramine and mols of paraformaldehyde, followed by the subsequent reaction with one mol of liquid dimer acid (Empol 1022) yielded a non-irritant viscous curing agent which cures an epoxy resin in about 30 minutes.
EXAMPLES l3l6 Proceeding as in Example 1 to prepare an aminealdehyde complex by heating the ingredients in a flask as described, and subsequently reacting the resulting aminealdehyde complex by slowly adding an acid or acid anhydride, and removing the water of reaction, for exam- 7 pie by applying reduced pressure to the fla'slc, a series of hardeners was formed having varying proportions of the acid constituent as shown in Table 1 below.
T able I Example No 13 14 15 16 Tetraethyleue pentamine, mols- 1 1 1 1 'Paraif-rmaldehyde, mols 1 1 1 1 Hexahydrophthalic Anhydride,
mols 0 0. 25 0.5 1 Viscosity, centipoises at 25 C 300 5, 600 296, 000 Solid 'trimer acid (Emery industries), oxalic, succinic, maleic,
EXAMPLE 17 One hundred parts by weight of an active 2,2 bis (4- hydroxyphenyl) propane-epichlorohydrin epoxy resin having an epoxy equivalent of 200 were mixed with 200 parts by weight of the hardener prepared as described in Example 7. T he gelling time at 25 C. was 30 minutes, and the composition was hardened completely in the usual manner.
While specific examples of non-irritant epoxy hardeners have been given by Way of illustration, it will be understood that many other combinations of equivalent ingredients may be reacted to give non-irritant hardening agents for epoxy resins, within the scope of the appended claims.
We claim:
1. A non-irritant hardening agent adapted for curing 2,2-bis (4-hydroxyphenyl) propane-epichlorohydrin epoxy resin compositions consisting essentially of the substantially anhydrous liquid reaction product of an aliphatic polyamine compound and an aldehyde, the ratio of amine to aldehyde being selected to retain a substantial proportion of reactive hydrogen in the product.
2. A non-irritant hardening agent adapted for curing epoxy resin compositions consisting essentially of the substantially anhydrous liquid reaction product of two mols of an aliphatic polyamlne compound and at least one mol of an aldehyde.
3. A non-irritant hardening agent adapted for curing 2,2-bis (4-hydroxyphenyl) propane-epichlorohydrin epoxy resin compositions consisting essentially of the co-reacted substantially anhydrous mixture of the liquid reaction product of an aliphatic polyamine with an aldehyde, and an acid constituent selected from the group consisting of aliphatic carboxylic acids, aromatic vcarboxylic acids, anhydrides of aliphatic carboxylic acids, and anhydrides of aromatic carboxylic acids; the ratio of acid anhydride or acid to the liquid reaction product being selected to retain a substantial proportion of reactive hydrogen in the hardening agent.
4. A non-irritant hardening agent adapted for curing 2,2 bis (4 hydroxyphenyl) propane epichlcrohydrin epoxy resin compositions consisting essentially of the coreacted substantially anhydrous mixture of the liquid reaction product of two mols or an aliphatic polyamine with at least one mole of. an aldehyde, and an acid constituent selected from the group consisting of aliphatic carboxylic acids, aromatic carboxylic acids, anhydrides of aliphatic carboxylic acids, and anhydrides of aromatic carboxylic acids, the ratio of the acid constituent to the amine-aldehyde reaction product being selected to produce a hardener agent of the desired viscosity and retained reactive hydrogen.
5. The hardening agent as defined in claim 2, in which the aldehyde is paraformaldehyde.
6. The hardening agent'as defined in claim 2, in which the aldehyde is furfuraldehyde.
7. The hardening agent as defined in claiml in which the aldehyde is paraformaldehyde and the polyamine is selected from the group consisting of ethylene diamine; hydrazine; li -propanediamine; l,2-propanediamine; 1,4- butanediamine; 'trimethylenediamine; tetramethylenediamine; diethylenetriamine; triethylene tetramine; te aethylenepe ntarnine; 3,3'-irninobispropylamine; 3,3 (methylimino) bispropylamine; 3-isopropylamincpropylamine; dimetl'iylaminopropylamine; diethylaminopropylamine;
ethylenebisoxypropylamine; methanediamine; and metaxylenediamine.
8. The non-irritant hardening agent defined in claim 4 in which the carboxylic acid constituent is hexahydrophthalic anhydride.
9. The non-irritant hardening agent defined in claim 4 in which the carboxylic acid constituent is succinic anhydride.
10. The non-irritant hardening agent defined in claim 4 in which the carboxylic acid constituent is acetic anhydride.
11. The non-irritant hardening agent defined in claim 4 in which the carboxylic acid consituent is liquid dimer acid.
12. A hardened epoxy resin product consisting essenfially of a 2,2-bis (4-hydroxyphenyl) propane-epichlorohydrin epoxy resin and a hardener consisting essentially of the substantially anhydrous liquid reaction product of one mol of an aliphatic polyamine and at least one mol of an aldehyde, the epoxy resin and the hardener being present in substantially stoichiometrie proportions based upon the epoxy equivalent.
13. A hardened epoxy resin product consisting essentially of a 2,2-bis (4-hydroxyphenyl propane-epichlorohydrin epoxy resin, and a hardener consisting essentially of a co-reacted substantially anhydrous liquid reaction product of an aliphatic polyamine with an aldehyde, and a carboxylic acid constituent selected from the group consisting of aliphatic carboxylic acids, aromatic carboxylic acids, anhydrides of alphatic carboxylic acids, and anhydrides of aromatic carboxylic acids, the epoxy resin and the hardener being present in substantially stoichiometric proportions based upon the epoxy equivalent.
14. A non-irritant hardening agent adapted for curing 2,2-bis (4-hydroxyphenyl) propane-epichlorohydrin epoxy resin compositions consisting essentially of the substantially anhydrous liquid reaction product of tetraethylene pentamine andparaformaldehyde.
References Cited in the file of this patent UNITED STATES PATENTS Treboux Feb. 10, 1942 2,511,913 Greenlee June 20, 1950

Claims (1)

12. A HARDENED EPOXY RESIN PRODUCT CONSISTING ESSENTIALLY OF A 2,2-BIS (4-HYDROXYPHENYL) PROPANE-EPICHLOROHYDRIN EPOXY RESIN AND A HARDENER CONSISTING ESSENTIALLY OF THE SUBSTANTIALLY ANHYDROUS LIQUID REACTION PRODUCT OF ONE MOL OF AN ALIPHATIC POLYAMINE AND AT LEAST ONE MOL OF AN ALDEHYDE, THE EPOXY RESIN AND THE HARDENER BEING PRESENT IN SUBSTANTIALLY STOICHIOMETRIC PROPORTIONS BASED UPON THE EPOXY EQUIVALENT.
US840788A 1959-09-18 1959-09-18 Curing agent comprising the reaction product of an aliphatic polyamine and an aldehyde, and epoxy resin cured therewith Expired - Lifetime US3026285A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US840788A US3026285A (en) 1959-09-18 1959-09-18 Curing agent comprising the reaction product of an aliphatic polyamine and an aldehyde, and epoxy resin cured therewith

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US840788A US3026285A (en) 1959-09-18 1959-09-18 Curing agent comprising the reaction product of an aliphatic polyamine and an aldehyde, and epoxy resin cured therewith

Publications (1)

Publication Number Publication Date
US3026285A true US3026285A (en) 1962-03-20

Family

ID=25283238

Family Applications (1)

Application Number Title Priority Date Filing Date
US840788A Expired - Lifetime US3026285A (en) 1959-09-18 1959-09-18 Curing agent comprising the reaction product of an aliphatic polyamine and an aldehyde, and epoxy resin cured therewith

Country Status (1)

Country Link
US (1) US3026285A (en)

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3261784A (en) * 1959-01-23 1966-07-19 Goldund Und Silber Scheideanst Process for altering the properties of high molecular weight halogen containing substances
US3315010A (en) * 1962-05-23 1967-04-18 Gen Aniline & Film Corp Mixture of an epoxy resin and an o-toluidine-aldehyde condensate
US3336247A (en) * 1961-08-07 1967-08-15 Hawley Products Co Formaldehyde-epoxidized polyepoxidepolyamine precondensate altering resins and process for preparing them
US3346519A (en) * 1964-11-12 1967-10-10 Hawley Products Co Process of adhering anionic and non-ionic substances to anionic substances
US3386953A (en) * 1963-08-26 1968-06-04 Gen Mills Inc Latent curing of epoxy resins
US3426097A (en) * 1965-08-24 1969-02-04 Gen Motors Corp Latent curing agents for epoxide polymers and polyurethanes
US3468830A (en) * 1966-08-26 1969-09-23 Pall Corp Curing of epoxide resins with the reaction product of an organic amine and an aldehyde,and curing and resin compositions and process
DE2724063A1 (en) * 1977-05-27 1978-12-07 Hoechst Ag DILUTION AGENT FOR HIGH MOLECULAR AMINES
US4131632A (en) * 1976-09-28 1978-12-26 Tokyo Shibaura Electric Co., Ltd. Heat-resistant resin compositions
GB2179950A (en) * 1985-09-03 1987-03-18 Permabond Adhesives Initiator compositions for two part acrylic adhesives
US4748083A (en) * 1986-01-29 1988-05-31 Sika Ag, Vorm. Kaspar Winkler & Co. Moisture curable composition
US4784797A (en) * 1984-03-29 1988-11-15 The Dow Chemical Company Process for inhibiting corrosion of ferrous metals
US4784796A (en) * 1984-03-29 1988-11-15 The Dow Chemical Company Corrosion inhibitors
US5264525A (en) * 1986-08-28 1993-11-23 National Starch And Chemical Investment Holding Corporation Initiator compositions for two part acrylic adhesives
WO2013081895A2 (en) 2011-12-01 2013-06-06 Dow Global Tecnologies LLC Liquid accelerator composition for hardeners
WO2016029038A1 (en) * 2014-08-21 2016-02-25 Hexion Inc. Curing compositions and methods of preparing

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2272783A (en) * 1938-09-22 1942-02-10 Firm Of J R Geigy A G Agents for improving the fastness of directly dyed cellulose fibers to water, acid bol, and wet ironing, and their manufacture
US2511913A (en) * 1950-06-20 Compositions of resinous epoxides

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2511913A (en) * 1950-06-20 Compositions of resinous epoxides
US2272783A (en) * 1938-09-22 1942-02-10 Firm Of J R Geigy A G Agents for improving the fastness of directly dyed cellulose fibers to water, acid bol, and wet ironing, and their manufacture

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3261784A (en) * 1959-01-23 1966-07-19 Goldund Und Silber Scheideanst Process for altering the properties of high molecular weight halogen containing substances
US3336247A (en) * 1961-08-07 1967-08-15 Hawley Products Co Formaldehyde-epoxidized polyepoxidepolyamine precondensate altering resins and process for preparing them
US3315010A (en) * 1962-05-23 1967-04-18 Gen Aniline & Film Corp Mixture of an epoxy resin and an o-toluidine-aldehyde condensate
US3386953A (en) * 1963-08-26 1968-06-04 Gen Mills Inc Latent curing of epoxy resins
US3346519A (en) * 1964-11-12 1967-10-10 Hawley Products Co Process of adhering anionic and non-ionic substances to anionic substances
US3426097A (en) * 1965-08-24 1969-02-04 Gen Motors Corp Latent curing agents for epoxide polymers and polyurethanes
US3468830A (en) * 1966-08-26 1969-09-23 Pall Corp Curing of epoxide resins with the reaction product of an organic amine and an aldehyde,and curing and resin compositions and process
US4131632A (en) * 1976-09-28 1978-12-26 Tokyo Shibaura Electric Co., Ltd. Heat-resistant resin compositions
DE2724063A1 (en) * 1977-05-27 1978-12-07 Hoechst Ag DILUTION AGENT FOR HIGH MOLECULAR AMINES
US4784797A (en) * 1984-03-29 1988-11-15 The Dow Chemical Company Process for inhibiting corrosion of ferrous metals
US4784796A (en) * 1984-03-29 1988-11-15 The Dow Chemical Company Corrosion inhibitors
GB2179950A (en) * 1985-09-03 1987-03-18 Permabond Adhesives Initiator compositions for two part acrylic adhesives
GB2179950B (en) * 1985-09-03 1989-08-16 Permabond Adhesives Initiator compositions for two part acrylic adhesives
US4748083A (en) * 1986-01-29 1988-05-31 Sika Ag, Vorm. Kaspar Winkler & Co. Moisture curable composition
US5264525A (en) * 1986-08-28 1993-11-23 National Starch And Chemical Investment Holding Corporation Initiator compositions for two part acrylic adhesives
WO2013081895A2 (en) 2011-12-01 2013-06-06 Dow Global Tecnologies LLC Liquid accelerator composition for hardeners
WO2016029038A1 (en) * 2014-08-21 2016-02-25 Hexion Inc. Curing compositions and methods of preparing
US9790313B2 (en) 2014-08-21 2017-10-17 Hexion Inc. Curing compositions and methods of preparing

Similar Documents

Publication Publication Date Title
US3026285A (en) Curing agent comprising the reaction product of an aliphatic polyamine and an aldehyde, and epoxy resin cured therewith
US3474056A (en) Curing agents for polyepoxides
US2651589A (en) Process for forming cured glycidyl ether resinous bonds between two solid surfaces
EP0000605B1 (en) Hardeners for aqueous dispersions of epoxy resins, their preparation and use
JPH0635503B2 (en) Diethyltoluenediamine curing agent system
US3489695A (en) Substituted imidazoles for curing epoxy resins
US3294743A (en) Epoxy ether resin-lactone compositions
US4397998A (en) Curable epoxy compositions suitable for use in RIM processes
US3956208A (en) Aqueous epoxy resin composition containing a fatty acid polyamide
US3673274A (en) Polymeric adhesive containing a polyepoxide, a carboxy terminated polybutadiene and a bis-2-oxazoline
WO1984000551A1 (en) Method for making phenol-formaldehyde-polyamine curing agents for epoxy resins
DE1100278B (en) Process for curing resinous epoxy compounds
JPS5835178B2 (en) Process for producing acrylic acid adducts of aminoamides of monomeric aliphatic compounds
US3948849A (en) Adhesive compositions
US2819233A (en) Curing of epoxide resins with a chelate
US2742448A (en) Epoxy resin compsotions containing titanate
US3496139A (en) Epoxy resins with reaction product of a polysiloxane and an amine
US3036975A (en) Rapid-curing epoxy resin compositions and method of making
US3188362A (en) Semi-rigid epoxy resin compositions and method
US3280074A (en) Monotertiary-diprimary triamines and the use thereof for curing epoxy resins
US3642649A (en) Low temperature tertiary amine accelerators
US3374186A (en) Curing polyepoxide compounds with a polyamine
US3316191A (en) Curing epoxy resins
Allen et al. Some characteristics of epoxide resin systems
US3753917A (en) Curing agent for epoxy resins to impart excellent solvent resistance